CN103923106A - Low-energy-gap and broad-absorption conjugated polymer and preparation method thereof - Google Patents

Low-energy-gap and broad-absorption conjugated polymer and preparation method thereof Download PDF

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CN103923106A
CN103923106A CN201410179009.3A CN201410179009A CN103923106A CN 103923106 A CN103923106 A CN 103923106A CN 201410179009 A CN201410179009 A CN 201410179009A CN 103923106 A CN103923106 A CN 103923106A
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diazosulfide
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李坚
姚尧
任强
汪称意
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Jiangyin Intellectual Property Operation Co., Ltd
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Abstract

The invention relates to the technical field of organic semiconductor preparation, and particularly relates to a low-energy-gap and broad-absorption conjugated polymer for solar cells and a preparation method thereof. The technical scheme adopted by the invention is as follows: by taking 3,4-ethylenedioxythiophene (EDOT) as an electron donating unit and 2,1,3 benzothiadiazole (BT) as an electron accepting unit, and through adopting a Heck coupling reaction, a novel D-A type conjugated monomer EDOTBT is prepared from the EDOT and the BT, the conjugated monomer has a relatively strong electron push-pull effect, a novel high-molecular-weight polymer can be prepared from the D-A type conjugated monomer through the Heck coupling reaction or a Suzuki coupling reaction, and the polymer has the characteristics of low band gap, broad absorption, relatively high optical conversion efficiency and good film forming property, can be used as an active layer of a polymer solar cell, and can be used for effectively increasing the energy conversion efficiency of the polymer solar cell, therefore, the conjugated polymer is suitable for being popularized and applied in polymer solar cells.

Description

Conjugated polymers that a kind of low energy gap length absorbs and preparation method thereof
Technical field
The present invention relates to organic semiconductor preparing technical field, be specially conjugated polymers that a kind of low energy gap length that can be applicable to solar cell absorbs and preparation method thereof.
Background technology
In recent years, the cost of manufacture that has due to polymer solar battery (PSC) is low, easy to prepare, the outstanding advantage of safety and environmental protection and sustainable developability etc. is day by day remarkable, and research circle for the research of polymer solar battery also gradually extensively and more deep.In prior art, the research emphasis of organic photovoltaic battery mainly concentrates in the problem of photoelectric transformation efficiency, for improving the photoelectric transformation efficiency of organic photovoltaic battery, researchist has the mutual low band gap polymers material mating between absorption spectrum and the sunlight emmission spectrum of requirement organic photovoltaic battery, these low band gap polymers materials generally have following features: (1) is narrow can bandwidth to be absorbed, and can catch more photon and improve short-circuit current; (2) crystalline texture, is convenient to obtain higher photoelectric transformation efficiency; (3) lower HOMO energy level, can improve the open circuit voltage (Voc) of polymer device; (4) moderate lumo energy, be convenient to and soccerballene between produce effective charge transfer, improve hole mobility and packing factor, an approach the most effective that meets above-mentioned requirements is introduced supplied for electronic unit (Donor) exactly and is subject to electronic unit (Acceptor) to form the polymkeric substance of D-A type structure in main polymer chain, for being subject between electronic unit that intramolecular charge can occur, shift the electronics releasability of supplied for electronic unit and be subject to the electronics receiving capability of electronic unit can affect electronic structure and the performance of D-A type polymkeric substance; In addition, the polymkeric substance of D-A type can be by selecting different electron-donating groups and electron-accepting group to regulate energy band, energy level and charge mobility.
The achievement in research of relevant low energy gap polymkeric substance of the prior art is as follows: the people (Macromolecules such as Jiang J M, 2011, 44 (23): 9155-9163.) synthesized novel low-energy zone crystalline polymer PTHBO, PBTTBO and PTTTBO, this article adopts the thiophene (TH) of electron rich, 2, the two thiophene (BT) of 2-and thienyl thiophene (TT) are for pushing away electronic unit, with 2 of electron deficiency, 1, 3-benzo oxadiazole is for drawing electronic unit, resulting polymers show and soccerballene between effective charge transfer and make the energy balance of polymkeric substance, reduced the HOMO energy level of polymkeric substance, show good thermostability simultaneously, high crystalline and wide absorption region.People (the Chemistry of Materials such as Zhang M, 2011,23 (18): the polymkeric substance of 4264-4270.) having prepared four kinds of D-A types, the benzene 1,4-Dithiapentalene (IDT) replacing with four dodecyls is for pushing away electronic unit, with the two thienyl thiazoles (BTz) of four kinds of different groups, two thiophene-thiazole base thiazoles (TTz), two thienyl tetrazine (TZ), two thienyl diazosulfide (DTBT), for drawing electronic unit, synthetic multipolymer is respectively PIDT-BTz, PIDT-TTz, PIDT-TZ and PIDT-DTBT.Wang M, Li C, Lv A, et al. (Polymer, 2012,53 (2): 324-332.) synthetic polymkeric substance is to using triphenylamine as electron donor, using the D-A type multipolymer of thieno-diazosulfide as electron-withdrawing group.
Summary of the invention
The object of the present invention is to provide a kind of D-A type conjugative monomer with stronger electronics push-pull effect and preparation method thereof, D-A type conjugative monomer preparation has low band gaps, wide absorption, has the feature high molecular new polymers of higher phototranstormation efficiency and good film-forming properties and the method for being made solar cell active coatings by these polymkeric substance thus.
The technical solution adopted for the present invention to solve the technical problems is: the D-A type conjugative monomer that a kind of low energy gap length absorbs, and the structural formula of this monomer is:
wherein, R is H, Cl, Br or I.
A preparation method for the D-A type conjugative monomer that low energy gap length absorbs, has following steps:
(1) in reaction vessel, add 3,4-ethylene dioxythiophene, 4,7-bis-is bromo-2,1,3-diazosulfide, catalyzer, part, weak base, then add solvent in container, and reactor is vacuumized to rear inflated with nitrogen, be heated to 90 ℃, stir lower reaction 12-48h;
(2) after reaction finishes, products therefrom is poured in distilled water and extracted separatory with methylene dichloride, wash three times, anhydrous magnesium sulfate drying, (wherein solid phase is alkali alumina to cross post, moving phase is toluene: methylene dichloride=1:1), with methanol extraction 3-5 time, vacuum drying treatment, obtains solid phase prod and is target product 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide (H-EDOTBT-H);
(3) by the target product of above-mentioned gained 4,7-bis-(3,4-ethylenedioxy thiophene) in-diazosulfide (H-EDOTBT-H), add N-halo succinimide, Glacial acetic acid, then add solvent in container, under lucifuge ice bath agitation condition, react 24-48h;
(4), after reaction finishes, after rotary evaporation is dry, with 1-Methyl-2-Pyrrolidone, dissolve, methanol extraction, filtered and recycled precipitation, vacuum drying treatment, obtains solid phase prod and is target product Cl-EDOTBT-Cl, Br-EDOTBT-Br or I-EDOTBT-I;
Wherein, 3,4-ethylenedioxy thiophene is as shown in structural formula I below: 4,7-bis-bromo-2,1,3-diazosulfide is as shown in structural formula II below, and D-A type conjugative monomer H-EDOTBT-H is as shown in structural formula III below, N-halo succinimide is as shown in structural formula IV below, and D-A type conjugative monomer Br-EDOTBT-Br is as shown in structural formula V below.
IV, wherein, A=Cl, Br, I, V.
Further, in described step (1), 3,4-ethylene dioxythiophene and 4,7-bis-are bromo-2,1, and the feed ratio of 3-diazosulfide is (2+x 1): 1, x 1for 0.1-0.5;
Catalyzer is palladium catalyst, and 3,4-ethylene dioxythiophene and 4,7-bis-are bromo-2,1, and the mol ratio of 3-diazosulfide total amount and catalyzer is 1:0.003-0.1;
Part is that Tetrabutyl amonium bromide, tricyclohexyl phosphine fluoroborate, tricyclohexyl phosphine, three are dredged a kind of in butyl phosphine, triphenylphosphine or triethylene diamines, and the mol ratio of part and catalyzer is 4-12:1;
A kind of in the four octyl group ammonium hydroxide aqueous solutions that the four hexyl ammonium hydroxide aqueous solutions that the tetramethylammonium hydroxide aqueous solution that weak base is salt of wormwood, Potassium ethanoate, massfraction is 5-50%, the TBAH aqueous solution that massfraction is 5-50%, the tetraethyl ammonium hydroxide aqueous solution that massfraction is 5-50%, the TPAOH aqueous solution, massfraction that massfraction is 5-50% are 5-50% or massfraction are 5-50%, the mol ratio of alkali and catalyzer is 30-80:1;
Solvent is DMF or N,N-dimethylacetamide, and its consumption is that 3,4-ethylene dioxythiophene and 4,7-bis-are bromo-2,1, and the volumetric molar concentration of 3-diazosulfide total amount is at 0.1-0.5mol/L.
Further preferably, described catalyzer is Pd (OA c) 2, PdCl 2or Pd (PPh (dppf) 3) 4in a kind of, 3,4-ethylene dioxythiophene and 4,7-bis-are bromo-2,1, the optimum molar proportioning of 3-diazosulfide total amount and catalyzer is 1:0.035.
Further, in described step (3), 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide (H-EDOTBT-H) is 1:(2+x with the feed ratio of N-halo succinimide 2), x 2for 0.1-5;
The mol ratio of Glacial acetic acid and 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide (H-EDOTBT-H) is 9:1;
Solvent is chloroform or tetrahydrofuran (THF), and its consumption is 4,7-bis-(3,4-ethylene dioxythiophene)-2,1, and the volumetric molar concentration of 3-diazosulfide (H-EDOTBT-H) and N-halo succinimide NBS total amount is at 0.1-5mol/L.
A polymkeric substance for the D-A type conjugative monomer that low energy gap length absorbs, the structural formula of this polymkeric substance is:
the number-average molecular weight of polymkeric substance is 1000-100000;
Wherein, n is 1-10; X is 0.05-0.95; R 3for H, Br or
Ar is or in a kind of, R 1, R 2for H or (CH 2) zCH 3, wherein z number is 1-11.
A preparation method for the polymkeric substance of the D-A type conjugative monomer that contains the absorption of low energy gap length, can be synthetic by two kinds of coupled reactions, and a kind of method is by Heck coupled reaction, and another kind of method is by Suzuki coupled reaction.
Conjugated polymers by the synthetic low energy gap of D-A type of Heck coupled reaction, has following steps:
(1) in reaction vessel, add 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (H-EDOTBT-H), 2,7-dibromo fluorenes or 1,4-dibromobenzene or 4,4 '-bis-is bromo-1,1 '-biphenyl or 4, a kind of, the catalyzer in 4 '-dibromo triphenylamine, part, weak base, in container, add solvent again, reaction vessel is vacuumized to rear inflated with nitrogen, be heated to 95 ℃, under agitation condition, react 12-48h;
(2) after reaction finishes, by products therefrom add successively methanol extraction, filtered and recycled precipitation, methylene dichloride dissolution precipitation thing, (wherein solid phase is silica gel to cross post, moving phase is methylene dichloride), Rotary Evaporators evaporation concentration, add methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product;
Wherein, 2,7-dibromo fluorenes, Isosorbide-5-Nitrae-dibromobenzene, 4,4 '-bis-is bromo-1,1 '-biphenyl, 4,4 '-dibromo triphenylamine respectively as shown in VI, VII, VIII, IX structural formula below, R wherein 1, R 2for H or (CH 2) zCH 3, wherein z number is 1-11,
Further, in described step (1), 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (H-EDOTBT-H) and 2,7-dibromo fluorenes or 1,4-dibromobenzene or 4,4 '-bis-is bromo-1,1 '-biphenyl or 4, and a kind of molar feed ratio in 4 '-dibromo triphenylamine is 0.5-1:1;
Catalyzer is palladium catalyst, 4,7-bis-(3,4-ethylenedioxy thiophene)-diazosulfide monomer (H-EDOTBT-H) and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-bis-bromo-1,1 '-biphenyl or 4, a kind of total amount in 4 '-dibromo triphenylamine and the mol ratio of catalyzer are 1:0.003-0.1;
Part is that Tetrabutyl amonium bromide, tricyclohexyl phosphine fluoroborate, tricyclohexyl phosphine, three are dredged a kind of in butyl phosphine, triphenylphosphine or triethylene diamines, and the mol ratio of part and catalyzer is 4-12:1;
Weak base is salt of wormwood, Potassium ethanoate, massfraction is the tetramethylammonium hydroxide aqueous solution of 5-50%, massfraction is the TBAH aqueous solution of 5-50%, massfraction is the tetraethyl ammonium hydroxide aqueous solution of 5-50%, massfraction is the TPAOH aqueous solution of 5-50%, massfraction is a kind of in the four hexyl ammonium hydroxide aqueous solutions of 5-50% or four octyl group ammonium hydroxide aqueous solutions that massfraction is 5-50%, alkali and 4, 7-bis-(3, 4-ethylenedioxy thiophene)-diazosulfide monomer and 2, 7-dibromo fluorenes or 1, 4-dibromobenzene or 4, 4 '-bis-bromo-1, 1 '-biphenyl or 4, the mol ratio of a kind of total amount in 4 '-dibromo triphenylamine is 4-12:1,
Solvent is N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, its consumption is 4,7-bis-(3,4-ethylenedioxy thiophene)-diazosulfide monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-bis-bromo-1,1 '-biphenyl or 4, the volumetric molar concentration of a kind of total amount in 4 '-dibromo triphenylamine is at 0.1-0.5mol/L.
Further preferably, described catalyzer is Pd (OA c) 2, PdCl 2or Pd (PPh (dppf) 3) 4in a kind of, 4,7-bis-(3,4-ethylenedioxy thiophene)-diazosulfide monomer (H-EDOTBT-H) and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-bis-is bromo-1,1 '-biphenyl or 4, and a kind of total amount in 4 '-dibromo triphenylamine and the best proportioning of catalyzer are 1:0.04.
A preparation method for the polymkeric substance of the conjugative monomer absorbing by the synthetic D-A type low energy gap length of Suzuki coupled reaction, has following steps:
(1) in reaction vessel, add 4 after bromination, 7-bis-(3, hypoboric acid ester, catalyzer, part, the weak base of 4-ethylenedioxy thiophene)-diazosulfide monomer (Br-EDOTBT-Br), fluorenes or benzene or biphenyl or triphenylamine, in container, add solvent again, reaction vessel is vacuumized to rear inflated with nitrogen, be heated to 95 ℃, stir lower reaction 12-48h; Add again phenylo boric acid reaction 2 hours, finally add bromobenzene reaction 2 hours;
(2) after reaction finishes, by products therefrom add successively methanol extraction, filtered and recycled precipitation, methylene dichloride dissolution precipitation thing, (wherein solid phase is silica gel to cross post, moving phase is methylene dichloride), Rotary Evaporators evaporation concentration, add methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product;
Wherein, the hypoboric acid ester of fluorenes or benzene or biphenyl or triphenylamine is specially: 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxa borine-bis-base)-9,9-bis-fluorenes, 1,4-two (4,4,5,5-tetramethyl--1,3,2-dioxa borine-bis-base)-benzene, 4,4 '-bis-(4,4,5,5-tetramethyl--1,3,2-dioxa borine-bis-base)-1,1 '-biphenyl and 4,4 '-bis-(4,4,5,5-tetramethyl--1,3,2-dioxa borine-bis-base) triphenylamine, its structural formula as shown in VI, VII, VIII, IX, R 1, R 2for H or (CH 2) zCH 3, wherein z number is 1-11,
Further, in described step (1), 4 after bromination, the feed ratio of the hypoboric acid ester of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (Br-EDOTBT-Br), fluorenes or benzene or biphenyl or triphenylamine is 1:1;
Catalyzer is palladium catalyst, 4 after bromination, and 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (Br-EDOTBT-Br) and fluorenes or the hypoboric acid ester total amount of benzene or biphenyl and the mol ratio of catalyzer are 1:0.003-0.1;
Part is a kind of in tricyclohexyl phosphine fluoroborate, tricyclohexyl phosphine, tri-butyl phosphine, triphenylphosphine or triethylene diamine, and the mol ratio of part and catalyzer is 4-12:1;
Weak base is that massfraction is the tetramethylammonium hydroxide aqueous solution of 5-50%, massfraction is the TBAH aqueous solution of 5-50%, massfraction is the tetraethyl ammonium hydroxide aqueous solution of 5-50%, massfraction is the TPAOH aqueous solution of 5-50%, massfraction is the four hexyl ammonium hydroxide aqueous solutions of 5-50%, massfraction is the four octyl group ammonium hydroxide aqueous solutions of 5-50%, a kind of in Potassium ethanoate or salt of wormwood, after weak base and bromination 4, 7-bis-(3, the mol ratio of the hypoboric acid ester total amount of 4-ethylenedioxy thiophene)-diazosulfide monomer (Br-EDOTBT-Br) and fluorenes or benzene or biphenyl or triphenylamine is 4-12:1,
Solvent is a kind of in benzene, toluene or dimethylbenzene, its consumption is 4 after bromination, the volumetric molar concentration of the hypoboric acid ester total amount of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (Br-EDOTBT-Br) and fluorenes or benzene or biphenyl or triphenylamine is at 0.1-0.5mol/L;
After the consumption of phenylo boric acid and bromination 4, the mol ratio of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (Br-EDOTBT-Br) is 1:1; The mol ratio of the hypoboric acid ester of the consumption of bromobenzene and fluorenes or benzene or biphenyl or triphenylamine is 1:1.
Further preferably, described catalyzer is Pd (OA c) 2, PdCl 2or Pd (PPh (dppf) 3) 4in a kind of, 4 after bromination, 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer (Br-EDOTBT-Br) and fluorenes or the hypoboric acid ester total amount of benzene or biphenyl and the best proportioning of catalyzer are 1:0.04.
The polymer application of the conjugative monomer that the low energy gap length that adopts technical scheme gained of the present invention is absorbed is in preparing organic solar batteries, and battery structure is: anode ITO/ hole transmission layer/active coating/(electron transfer layer)/negative electrode Al; Concrete preparation method is as follows:
(1) substrate of glass that contains ITO is cleaned up, at ITO spin coating PEDOT/PSS solution, spin coating dries after annealing and obtains hole transmission layer;
(2) by the low energy gap conjugated polymers of gained of the present invention and tetrabutyl titanate (TBTT) or [6,6]-phenyl C 61methyl-butyrate (PCBM) blend is dissolved in chloroform solvent and is spin-coated on hole transmission layer, and spin coating dries after annealing and obtains active coating; Conjugated polymers and TBTT or PCBM mass ratio are 1:1-20;
(3) by the structure obtaining at vacuum condition (1 * 10 -4pa) the lower thick Al of evaporation one deck 100nm.
Spin coating described in step (1) and step (2) is divided into two steps, and the first step rotating speed is 750r/min, and the time is 10s, and second step rotating speed is 3000-4500r/min, and the time is 25-30s, and spin coating environment is air or nitrogen; Annealing temperature is 130-200 ℃, and annealing time is 10-30min, and anneal environment is air.
Beneficial effect: the present invention is with 3, 4-ethylene two oxy thiophene (EDOT) is supplied for electronic unit, 2, 1, 3 diazosulfides (BT) are for being subject to electronic unit, adopt Heck coupled reaction to prepare novel D-A type conjugative monomer 4 by EDOT and BT, 7-bis-(3, 4-ethylenedioxy thiophene)-2, 1, 3-diazosulfide (EDOTBT), this D-A type conjugative monomer has stronger electronics push-pull effect, can by above-mentioned D-A type conjugative monomer, prepare high molecular new polymers by Heck coupled reaction or Suzuki coupled reaction, these polymkeric substance have low band gaps, wide absorption, the feature of higher phototranstormation efficiency and good film-forming properties, can be used as the active coating of polymer solar battery, can effectively improve the effciency of energy transfer (PCE) of polymer solar battery, suitablely in polymer solar battery, apply.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described;
Fig. 1 is conjugative monomer 4 in embodiments of the invention 1,7-bis-(3,4-ethylene dioxythiophene)-2,1,3-diazosulfide H-EDOTBT-H's 1hNMR;
Fig. 2 is D-A type conjugative monomer 4 in embodiments of the invention 2,7-bis-(3,4-ethylene dioxythiophene)-2,1, Br-EDOTBT-Br after 3-diazosulfide bromination 1hNMR;
Fig. 3 is polymer P F6EDOTBT in embodiments of the invention 3 1hNMR;
Fig. 4 is the uv-absorbing figure of polymer P F6EDOTBT in embodiments of the invention 3;
Fig. 5 is the uv-absorbing figure of polymer P F8EDOTBT in embodiments of the invention 4.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited to the present embodiment.Embodiment mono-
4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide conjugative monomer H-EDOTBT-H's is synthetic:
Reactions steps:
Thermometer is being housed, in the there-necked flask of the 100ml of stirrer, is quantitatively adding 4 of 0.147g (0.5mmol), 7-bis-bromo-2, Pd (the OA of 3,4 ethylenedioxy thiophenes of 1,3-diazosulfide, 0.142g (1mmol), 0.0118g (0.0525mmol) c) 2, 0.498g (1.5mmol) the salt of wormwood K of Tetrabutyl amonium bromide TBAB, 0.3628g (2.625mmol) 2cO 3, 8ml DMF DMF.Mixed 95 ℃ of reaction 12h stopped reaction under nitrogen atmosphere.After reaction finishes, products therefrom is poured in distilled water and extracted separatory with methyl chloride, wash three times, anhydrous magnesium sulfate drying, cross post (wherein solid phase is alkali alumina, and moving phase is toluene: methylene dichloride=1:1), with methanol extraction for several times, vacuum drying treatment, finally obtains solid phase prod and is target product.Vacuum-drying 24h under 80 ℃ of conditions, productive rate is 40%, to product 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide conjugative monomer H-EDOTBT-H's 1hNMR is shown in Fig. 1.
Embodiment bis-
D-A type conjugative monomer Br-EDOTBT-Br's is synthetic:
Reactions steps:
Thermometer is being housed, in the there-necked flask of the 100ml of stirrer, quantitatively add 4 of 0.208g (0.5mmol), the N-bromosuccinimide of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide H-EDOTBT-H, 0.1780g (1mmol), the acetic acid of 0.27g (4.5mmol), the chloroform of 12ml.Lucifuge ice bath stirs lower reaction more than 24 hours, after reaction finishes, and methanol extraction, filtered and recycled precipitation, vacuum drying treatment, finally obtains solid phase prod and is target product.Vacuum-drying 24h under 100 ℃ of conditions, productive rate is 80%.Fig. 2 is the D-A type conjugative monomer Br-EDOTBT-Br of synthesized in the present embodiment 1hNMR.
Embodiment tri-
The copolymer p F6EDOTBT of D-A type conjugative monomer H-EDOTBT-H and 9,9-dihexyl fluorenes:
Polymerization procedure:
Thermometer is being housed, in the there-necked flask of the 100ml of stirrer, the D-A type conjugative monomer H-EDOTBT-H, the 0.2952g (0.6mmol) 2 that quantitatively add 0.2496g (0.6mmol), 7-dibromo 9, the Pd (OA of 9-dihexyl fluorenes, 0.0008g (0.0036mmol) c) 2, 0.0048g (0.0144mmol) Tetrabutyl amonium bromide TBAB, 0.6634g (4.8mmol) salt of wormwood K 2cO 3and 12mlN, the mixed solvent of dinethylformamide DMF.Mixed stopped reaction after 90 ℃ of reaction 12h under nitrogen atmosphere.Reaction finishes rear methanol extraction, filtered and recycled precipitation, with crossing post after methylene dichloride dissolving, (wherein solid phase is silica gel again, moving phase is methylene dichloride), Rotary Evaporators is concentrated, add methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product.The dry 24h of vacuum drying oven under 80 ℃ of conditions, productive rate is 54.2%.Fig. 3 is the polymer P F6EDOTBT of synthesized in the present embodiment 1hNMR, Fig. 4 is the uv-absorbing figure of polymer P F6EDOTBT.
Embodiment tetra-
The copolymer p F8EDOTBT of D-A type conjugative monomer Br-EDOTBT-Br and 9,9-dioctyl fluorene:
Polymerization procedure:
Thermometer is being housed, in the there-necked flask of the 100ml of stirrer, quantitatively add 0.3444g (0.6mmol) D-A type conjugative monomer Br-EDOTBT-Br, 0.38556g (0.6mmol), 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxa borine-bis-base)-9, the Pd (OA of 9-dioctyl fluorene, 0.004g (0.018mmol) c) 2, 0.022g (0.20mmol) triethylene diamine DABCO, 8ml massfraction be the mixed solvent of 25%Et4NOH and 10ml toluene, mixed stopped reaction after 90 ℃ of reaction 12h under nitrogen atmosphere.Add again 0.0612g (0.5mmol) phenylo boric acid reaction 2h, finally add 0.078g (0.5mmol) bromobenzene reaction 2h.Methanol extraction, filtered and recycled are crossed post after precipitating, dissolving with methylene dichloride, and (wherein solid phase is silica gel, moving phase is methylene dichloride), Rotary Evaporators is concentrated, add methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product.The dry 24h of vacuum drying oven under 80 ℃ of conditions, productive rate is that 58.4%, Fig. 5 is the uv-absorbing figure of target product PF8EDOTBT.
Table 1 is the optical property data of embodiment tri-and embodiment tetra-gained multipolymers
Embodiment five
The multipolymer of D-A type conjugative monomer H-EDOTBT-H and biphenyl:
Polymerization procedure:
Thermometer is being housed, in the there-necked flask of the 100ml of stirrer, quantitatively add 0.2496g (0.6mmol) D-A type conjugative monomer H-EDOTBT-H, 0.1872g (0.6mmol), 4,4 '-bis-bromo-1, the Pd (OA of 1 '-biphenyl, 0.0094g (0.042mmol) c) 2, 0.0619g (0.168mmol) tricyclohexyl phosphine fluoroborate, 8ml massfraction be the 25% TPAOH aqueous solution and 10mlN, the mixed solvent of N-N,N-DIMETHYLACETAMIDE DMA.Mixed stopped reaction after 90 ℃ of reaction 12h under nitrogen atmosphere.Reaction finishes rear methanol extraction, filtered and recycled precipitation, with crossing post after methylene dichloride dissolving, (wherein solid phase is silica gel again, moving phase is methylene dichloride), Rotary Evaporators is concentrated, add methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product, the dry 24h of vacuum drying oven under 80 ℃ of conditions, productive rate is 53.4%.
Embodiment six
The multipolymer of D-A type conjugative monomer Br-EDOTBT-Br and benzene:
Polymerization procedure:
Thermometer is being housed, in the there-necked flask of the 100ml of stirrer, quantitatively add 0.3444g (0.6mmol) D-A type conjugative monomer Br-EDOTBT-Br, 0.198g (0.6mmol), 1,4-two (4,4,5,5-tetramethyl--1,3,2-dioxa borine-bis-base) Pd (PPh of-benzene, 0.028g (0.018mmol) 3) 4, 0.022g (0.20mmol) triethylene diamine DABCO, 8ml massfraction be 25%Et 4the mixed solvent of NOH and 10ml toluene.Mixed stopped reaction after 90 ℃ of reaction 12h under nitrogen atmosphere.Add again 0.0612g (0.5mmol) phenylo boric acid reaction 2h, finally add 0.078g (0.5mmol) bromobenzene reaction 2h.Methanol extraction, filtered and recycled are crossed post after precipitating, dissolving with methylene dichloride, and (wherein solid phase is silica gel, moving phase is methylene dichloride), Rotary Evaporators is concentrated, add methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product.The dry 24h of vacuum drying oven under 80 ℃ of conditions, productive rate is 56.8%.
Embodiment seven
The multipolymer of D-A type conjugative monomer Br-EDOTBT-Br and triphenylamine:
Polymerization procedure:
Thermometer is being housed, in the there-necked flask of the 100ml of stirrer, quantitatively add 0.3444g (0.6mmol) D-A type Br-EDOTBT-Br, 0.2982g (0.6mmol), 4,4 '-bis-(4,4,5,5-tetramethyl--1,3,2-dioxa borine-bis-base) Pd (OA of triphenylamine, 0.0269g (0.12mmol) c) 2, 0.1615g (1.44mmol) triethylene diamine DABCO, 12ml massfraction be the mixed solvent of 25% Tetramethylammonium hydroxide TMAOH and 30ml toluene.Mixed stopped reaction after 90 ℃ of reaction 12h under nitrogen atmosphere.Add again 0.0612g (0.5mmol) phenylo boric acid reaction 2h, finally add 0.078g (0.5mmol) bromobenzene reaction 2h.Methanol extraction, filtered and recycled are crossed post after precipitating, dissolving with methylene dichloride, and (wherein solid phase is silica gel, moving phase is methylene dichloride), Rotary Evaporators is concentrated, add methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product.The dry 24h of vacuum drying oven under 80 ℃ of conditions, productive rate is 56.8%.
Embodiment eight
The organic solar batteries that the structure of preparation is ITO/PSS/PEDOT/PF6EDOTBT:PCBM/Al, step is as follows:
(1) PSS/PEDOT is paved with on the ITO surface cleaning up, by spin coating, dries, spin coating is divided into two steps: the first step is 750 revs/min at rotating speed, spin coating 10s; Second step is 3400 revs/min at rotating speed, spin coating 30s, and the 30min that anneals in 120 ℃ of air after finishing, thickness is: 100nm.Obtain organic solar batteries hole transmission layer;
(2) after copolymer p F6EDOTBT above-described embodiment being obtained joins in chloroform, add PCBM stir with 0.45um filter filter (PF6EDOTBT and PCBM mass ratio: 1:1), spin coating (the first rotating speed 750r/min, 10s; Second turns 3900r/min, 30s) on the hole transmission layer preparing, spin coating finishes rear 120 ℃ of 10min that anneal in air.Thickness is 100nm, obtains the active coating of battery;
(3) by the structure obtaining at vacuum condition (1 * 10 -4pa) the lower thick Al of evaporation one deck 100nm.The photovoltaic performance parameter testing of gained solar cell the results are shown in Table 2.
The photovoltaic test result of table 2 solar cell

Claims (10)

1. the D-A type conjugative monomer that low energy gap length absorbs, is characterized in that: the structural formula of described monomer is:
wherein, R is H, Cl, Br or I.
2. the preparation method of the D-A type conjugative monomer that low energy gap length according to claim 1 absorbs, is characterized in that: this preparation method has following steps:
(1) in reaction vessel, add 3,4-ethylene dioxythiophene, 4,7-bis-is bromo-2,1,3-diazosulfide, catalyzer, part, weak base, then add solvent in container, and reactor is vacuumized to rear inflated with nitrogen, be heated to 90 ℃, stir lower reaction 12-48h;
(2) after reaction finishes, products therefrom is poured in distilled water and extracted separatory with methylene dichloride, wash three times, anhydrous magnesium sulfate drying, crosses post, uses methanol extraction 3-5 time, vacuum drying treatment, obtain solid phase prod and be target product 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide;
(3) by the target product of above-mentioned gained 4, in 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide, add N-halo succinimide, Glacial acetic acid, then add solvent in container, under lucifuge ice bath agitation condition, react 24-48h;
(4), after reaction finishes, after rotary evaporation is dry, with 1-Methyl-2-Pyrrolidone, dissolve, methanol extraction, filtered and recycled precipitation, vacuum drying treatment, obtains solid phase prod and is target product Cl-EDOTBT-Cl, Br-EDOTBT-Br or I-EDOTBT-I.
3. the preparation method of the D-A type conjugative monomer that low energy gap length according to claim 2 absorbs, is characterized in that: in described step (1), 3,4-ethylene dioxythiophene and 4,7-bis-are bromo-2,1, and the feed ratio of 3-diazosulfide is (2+x 1): 1, x 1for 0.1-0.5;
Catalyzer is palladium catalyst, and 3,4-ethylene dioxythiophene and 4,7-bis-are bromo-2,1, and the mol ratio of 3-diazosulfide total amount and catalyzer is 1:0.003-0.1;
Part is that Tetrabutyl amonium bromide, tricyclohexyl phosphine fluoroborate, tricyclohexyl phosphine, three are dredged a kind of in butyl phosphine, triphenylphosphine or triethylene diamines, and the mol ratio of part and catalyzer is 4-12:1;
A kind of in the four octyl group ammonium hydroxide aqueous solutions that the four hexyl ammonium hydroxide aqueous solutions that the tetramethylammonium hydroxide aqueous solution that weak base is salt of wormwood, Potassium ethanoate, massfraction is 5-50%, the TBAH aqueous solution that massfraction is 5-50%, the tetraethyl ammonium hydroxide aqueous solution that massfraction is 5-50%, the TPAOH aqueous solution, massfraction that massfraction is 5-50% are 5-50% or massfraction are 5-50%, the mol ratio of alkali and catalyzer is 30-80:1;
Solvent is DMF or N,N-dimethylacetamide, and its consumption is that 3,4-ethylene dioxythiophene and 4,7-bis-are bromo-2,1, and the volumetric molar concentration of 3-diazosulfide total amount is at 0.1-0.5mol/L;
In described step (3), the feed ratio of 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide and N-halo succinimide is 1:(2+x 2), x 2for 0.1-5;
The mol ratio of Glacial acetic acid and 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide is 9:1;
Solvent is chloroform or tetrahydrofuran (THF), and its consumption is 4,7-bis-(3,4-ethylene dioxythiophene)-2,1, and the volumetric molar concentration of 3-diazosulfide and N-halo succinimide NBS total amount is at 0.1-5mol/L.
4. the preparation method of the D-A type conjugative monomer that low energy gap length according to claim 3 absorbs, is characterized in that: described catalyzer is Pd (OA c) 2, PdCl 2or Pd (PPh (dppf) 3) 4in a kind of, 3,4-ethylene dioxythiophene and 4,7-bis-are bromo-2,1, the optimum molar proportioning of 3-diazosulfide total amount and catalyzer is 1:0.035.
5. a polymkeric substance that contains the D-A type conjugative monomer of low energy gap length absorption claimed in claim 1, is characterized in that: the structural formula of this polymkeric substance is:
the number-average molecular weight of polymkeric substance is 1000-100000;
Wherein, n is 1-10; X is 0.05-0.95; R 3for H, Br or
Ar is or in a kind of, R 1, R 2for H or (CH 2) zCH 3, wherein z number is 1-11.
6. the preparation method of the polymkeric substance that contains the D-A type conjugative monomer that low energy gap length absorbs according to claim 5, is characterized in that: this preparation method has following steps:
(1) in reaction vessel, add 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer, 2,7-dibromo fluorenes or 1,4-dibromobenzene or 4,4 '-bis-is bromo-1,1 '-biphenyl or 4, a kind of, the catalyzer in 4 '-dibromo triphenylamine, part, weak base, in container, add solvent again, reaction vessel is vacuumized to rear inflated with nitrogen, be heated to 95 ℃, under agitation condition, react 12-48h;
(2) after reaction finishes, products therefrom is added successively to methanol extraction, filtered and recycled precipitation, methylene dichloride dissolution precipitation thing, mistake post, Rotary Evaporators evaporation concentration, adds methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product.
7. the preparation method of the polymkeric substance that contains the D-A type conjugative monomer that low energy gap length absorbs according to claim 6, it is characterized in that: in described step (1), 4,7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer and 2,7-dibromo fluorenes or 1,4-dibromobenzene or 4,4 '-bis-is bromo-1,1 '-biphenyl or 4, and a kind of molar feed ratio in 4 '-dibromo triphenylamine is 0.5-1:1;
Catalyzer is palladium catalyst, and 4,7-bis-(3,4-ethylenedioxy thiophene)-diazosulfide monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-bis-is bromo-1,1 '-biphenyl or 4, and a kind of total amount in 4 '-dibromo triphenylamine and the mol ratio of catalyzer are 1:0.003-0.1;
Part is that Tetrabutyl amonium bromide, tricyclohexyl phosphine fluoroborate, tricyclohexyl phosphine, three are dredged a kind of in butyl phosphine, triphenylphosphine or triethylene diamines, and the mol ratio of part and catalyzer is 4-12:1;
Weak base is salt of wormwood, Potassium ethanoate, massfraction is the tetramethylammonium hydroxide aqueous solution of 5-50%, massfraction is the TBAH aqueous solution of 5-50%, massfraction is the tetraethyl ammonium hydroxide aqueous solution of 5-50%, massfraction is the TPAOH aqueous solution of 5-50%, massfraction is a kind of in the four hexyl ammonium hydroxide aqueous solutions of 5-50% or four octyl group ammonium hydroxide aqueous solutions that massfraction is 5-50%, alkali and 4, 7-bis-(3, 4-ethylenedioxy thiophene)-diazosulfide monomer and 2, 7-dibromo fluorenes or 1, 4-dibromobenzene or 4, 4 '-bis-bromo-1, 1 '-biphenyl or 4, the mol ratio of a kind of total amount in 4 '-dibromo triphenylamine is 4-12:1,
Solvent is N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, its consumption is 4,7-bis-(3,4-ethylenedioxy thiophene)-diazosulfide monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-bis-bromo-1,1 '-biphenyl or 4, the volumetric molar concentration of a kind of total amount in 4 '-dibromo triphenylamine is at 0.1-0.5mol/L.
8. the preparation method of the polymkeric substance of the D-A type conjugative monomer that contains the absorption of low energy gap length according to claim 7, is characterized in that: described catalyzer is Pd (OA c) 2, PdCl 2or Pd (PPh (dppf) 3) 4in a kind of, 4,7-bis-(3,4-ethylenedioxy thiophene)-diazosulfide monomer and 2,7-dibromo fluorenes or Isosorbide-5-Nitrae-dibromobenzene or 4,4 '-bis-is bromo-1,1 '-biphenyl or 4, and a kind of total amount in 4 '-dibromo triphenylamine and the best proportioning of catalyzer are 1:0.04.
9. the preparation method of the polymkeric substance that contains the D-A type conjugative monomer that low energy gap length absorbs according to claim 5, is characterized in that: this preparation method has following steps:
(1) in reaction vessel, add 4 after bromination, 7-bis-(3, hypoboric acid ester, catalyzer, part, the weak base of 4-ethylenedioxy thiophene)-diazosulfide monomer, fluorenes or benzene or biphenyl or triphenylamine, in container, add solvent again, reaction vessel is vacuumized to rear inflated with nitrogen, be heated to 95 ℃, stir lower reaction 12-48h; Add again phenylo boric acid reaction 2h, finally add bromobenzene reaction 2h;
(2) after reaction finishes, products therefrom is added successively to methanol extraction, filtered and recycled precipitation, methylene dichloride dissolution precipitation thing, mistake post, Rotary Evaporators evaporation concentration, adds methanol extraction, filtered and recycled precipitation, vacuum drying treatment again, finally obtain solid phase prod and be target product.
10. the preparation method of the polymkeric substance that contains the D-A type conjugative monomer that low energy gap length absorbs according to claim 9, it is characterized in that: in described step (1), after bromination 4, the feed ratio of the hypoboric acid ester of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer, fluorenes or benzene or biphenyl or triphenylamine is 1:1;
Catalyzer is palladium catalyst, 4 after bromination, and the hypoboric acid ester total amount of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer and fluorenes or benzene or biphenyl and the mol ratio of catalyzer are 1:0.003-0.1;
Part is a kind of in tricyclohexyl phosphine fluoroborate, tricyclohexyl phosphine, tri-butyl phosphine, triphenylphosphine or triethylene diamine, and the mol ratio of part and catalyzer is 4-12:1;
Weak base is that massfraction is the tetramethylammonium hydroxide aqueous solution of 5-50%, massfraction is the TBAH aqueous solution of 5-50%, massfraction is the tetraethyl ammonium hydroxide aqueous solution of 5-50%, massfraction is the TPAOH aqueous solution of 5-50%, massfraction is the four hexyl ammonium hydroxide aqueous solutions of 5-50%, massfraction is the four octyl group ammonium hydroxide aqueous solutions of 5-50%, a kind of in Potassium ethanoate or salt of wormwood, after weak base and bromination 4, 7-bis-(3, the mol ratio of the hypoboric acid ester total amount of 4-ethylenedioxy thiophene)-diazosulfide monomer and fluorenes or benzene or biphenyl or triphenylamine is 4-12:1,
Solvent is a kind of in benzene, toluene or dimethylbenzene, and its consumption is 4 after bromination, and the volumetric molar concentration of the hypoboric acid ester total amount of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer and fluorenes or benzene or biphenyl or triphenylamine is at 0.1-0.5mol/L;
After the consumption of phenylo boric acid and bromination 4, the mol ratio of 7-bis-(3,4-ethylene dioxythiophene)-diazosulfide monomer is 1:1; The mol ratio of the hypoboric acid ester of the consumption of bromobenzene and fluorenes or benzene or biphenyl or triphenylamine is 1:1.
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